JP3002170B2 - Production method of high quality wood vinegar liquid raw material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention removes formaldehyde and methanol, which are biologically harmful components present in crude wood vinegar and bamboo vinegar, and contains active ingredients such as flavanols, tannins, polyphenols, cresols and cresols. Production of high-quality wood vinegar and high-quality bamboo vinegar (collectively referred to as high-quality crude wood vinegar in the present invention);
Cosmetics using this as a raw material (for cleaning, hair, foundation, makeup, aroma, sunburn / sunscreen, nails, eyeliner, lips, oral cavity, bathing), therapeutic agent for superficial skin / mucosal infections (pharmaceuticals, pharmaceuticals) Quasi-drugs) and foods such as soft drinks.

[0002]

2. Description of the Related Art Coarse wood vinegar used in the present invention refers to bark and trees. Coarse bamboo vinegar refers to an aqueous solution formed by cooling smoke generated when carbonizing bamboo such as bamboo. And
The chemical composition varies slightly depending on the type of raw wood to be carbonized and the type of bamboo, but in the case of crude wood vinegar, typical ones are acetic acid, propionic acid, butyric acid, methanol, formaldehyde, phenol, furfural, cresol, Cresol and the like. The crude bamboo vinegar has almost the same components.

As shown in the above components, the crude wood vinegar solution and the crude bamboo vinegar solution contain formaldehyde and methanol as biologically harmful components. Therefore, unless these harmful components are removed, cosmetics, pharmaceuticals, Cannot be used as food.

Conventionally, cosmetics using wood vinegar and bamboo vinegar,
R & D of food additives has been carried out, but there is no method to remove active ingredients such as phenol, tannin, and flavanol, and to remove biologically harmful components.Wood vinegar and bamboo vinegar are currently used in cosmetics research. However, no products approved by the Ministry of Health are available on the market.

[0005] Recently, soaps and cosmetics using wood vinegar have been marketed, but only the wood vinegar containing formaldehyde and methanol is added to cosmetic materials produced by a usual method.

[0006]

It is well known that wood vinegar and bamboo vinegar have long contained tannins (phenols are also a component thereof) that repair wounds on the skin and increase moisture. As a matter of fact, at the same time, several hundred ppm of formaldehyde and methanol, which are biologically harmful components, are contained, which has been a major obstacle to using them as cosmetics, pharmaceuticals, and foods.

[0007] Wood vinegar contains tar and carcinogenic substance such as benpyrene. According to the research and development of wood vinegar so far, it has been found that the removal, deodorization, and decolorization of these tar and benchpyrene are considered. There are many.

[0008] Wood vinegar and bamboo vinegar also contain tens of percent of a strongly acidic substance such as acetic acid, which causes a burning sensation when the wood vinegar is applied to the skin.

The present invention provides a raw material for a "body-friendly" high-quality wood vinegar and a high-quality bamboo vinegar containing an active ingredient, which removes the aforementioned biologically harmful components contained in the crude wood vinegar and the crude bamboo vinegar. To provide.

[0010]

That is, the present invention relates to a method of contacting a crude wood vinegar solution with activated carbon powder under acidic condition of pH 2.5 or less, and adsorbing the active ingredient in the crude wood vinegar solution to the activated carbon. Formaldehyde and methanol are washed off with water, and the active ingredient is eluted in a mixed solvent phase in which the mixing ratio of ethyl alcohol and ethyl acetate is in the range of 1: 9 to 3: 7, and the organic solvent phase is evaporated to dryness. The method for producing a high quality wood vinegar liquid raw material which does not contain methyl alcohol and formaldehyde , characterized by the following characteristics.

In the above method, the mixing ratio of ethyl alcohol to ethyl acetate is preferably in the range of 1: 9 to 3: 7.

The high-quality wood vinegar liquid produced by the above method is
A product dissolved in a 0 to 50% aqueous solution of ethyl alcohol or a squalane containing a surfactant (hereinafter abbreviated as squalane) or a 35 to 50% aqueous solution of glycerin is useful as a high quality wood vinegar liquid cosmetic.

Furthermore, the high-quality wood vinegar liquid raw material produced by the above method is used for superficial skin / mucosa Staphylococcus aureus, MRSA infection,
It is useful as a topical antimicrobial agent for superficial skin / mucosa Pseudomonas aeruginosa infection and superficial skin / mucosal tinea fungi.

Furthermore, the high-quality wood vinegar liquid raw material produced by the above method is useful as an oral cosmetic utilizing the antibacterial action against various pathogenic microorganisms.

Further, it is also useful as a food containing flavanol, phenol and tannin contained in the high-quality wood vinegar liquid produced by the above method.

Further, cosmetics containing the high-quality wood vinegar liquid raw material obtained by the method of the present invention in the range of 1 to 50% by weight,
It is also useful as a quasi drug and a food additive for sterilization.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The crude wood vinegar used in the production of the high-quality wood vinegar liquid raw material of the present invention is, in the case of crude wood vinegar, a dry distillate obtained in the process of carbonizing trees and bark. The case (1) is a dry distillate obtained in the process of carbonizing an adult bamboo, and any commonly used production method can be used.

Such a crude wood vinegar solution usually contains the above-mentioned chemical components, and is generally about 1.7 to 2.5% by weight as a total amount of solid components and volatile components. Is an aqueous solution of brown color with smoked odor and sourness containing the chemical components of

In the present invention, in order to produce a high-quality wood vinegar liquid raw material using activated carbon, 0.5 to 3.0 parts by weight of activated carbon, preferably 0.5 to 3.0 parts by weight, per 100 parts by weight of crude wood vinegar liquid.
Add 1.0 part by weight and adsorb under sufficient stirring conditions.
Activated carbon to be employed can be employed as long as it is a commonly used high-quality one, but the pH at the time of adsorption of the crude wood vinegar solution needs to be 2.5 or less. When the pH at the time of adsorption exceeds 2.5, the object of the present invention for efficiently adsorbing and separating the active ingredient in the crude wood vinegar solution is not achieved.

The activated carbon adsorbate and the liquid phase of the crude wood vinegar solution are separated by suction filtration using a solid-liquid separation device usually used, for example, a filter having a pore size of 0.8 μm. The separated activated carbon adsorbate phase is 20 to
Dispersed in 50 parts by weight, preferably 20 to 40 parts by weight of purified water, and subjected to suction filtration to obtain an activated carbon adsorbate of a crude wood complex solution.

The activated carbon adsorbate of the crude wood vinegar is then brought into contact with an organic solvent to extract useful substances from the crude wood vinegar. The organic solvent used in the present invention is a mixed solvent of ethyl alcohol and ethyl acetate, and in some cases, an organic solvent such as acetone, chloroform, chlorobenzene, and toluene may be used in a range that does not impair the effects of the present invention. Absent. As for the mixing ratio of ethyl alcohol and ethyl acetate, for example, a mixed solvent in the range of 1: 9 to 3: 7 is preferably used. The amount of these organic solvents used is 100 parts by weight of activated carbon adsorbate (converted as solids excluding water)
In the range of 250 to 1000 parts by weight, and a method of dividing and extracting a plurality of times can be adopted. Although the temperature condition at the time of extraction is generally sufficient even at a temperature around room temperature, it can be heated.

In the above-mentioned mixing ratio of ethyl alcohol and ethyl acetate, when the amount of ethyl alcohol is smaller than the amount of ethyl acetate, contact between the activated carbon adsorbing the active ingredient of the crude wood vinegar and ethyl acetate is not possible. The active ingredient is not sufficiently transferred to the organic solvent phase. Also, when the amount of ethyl alcohol is larger than that of ethyl acetate, the wood tar adsorbed on the activated carbon tends to migrate to the organic solvent phase, which causes inconvenience. Including a specified amount of ethyl alcohol also has the advantage of facilitating the recovery of ethyl acetate after use by distillation.

The organic solvent phase obtained by extracting the active ingredient of the crude wood vinegar solution from the activated carbon adsorbate with an organic solvent is separated from the activated carbon extraction residual phase by a conventional method such as suction filtration. The separated organic solvent phase is then evaporated to dryness by employing, for example, a rotary evaporator to obtain a high-quality wood vinegar liquid raw material which is separated from the crude wood vinegar by adsorption with activated carbon.

The high-quality bamboo vinegar raw material produced according to the present invention includes hot water, ethanol, diethyl ether,
It is soluble in organic solvents such as n-hexane, chloroform, ethyl acetate, and acetone, and is soluble in jojoba oil, squalane, and glycerin, and does not contain acetic acid, propionic acid, methyl alcohol, formaldehyde, and furfural.

The high-quality wood vinegar liquid raw material of the present invention obtained by the above-mentioned method is used by dissolving it in the above-mentioned solvent according to the purpose of use. For example, as a high quality wood vinegar liquid cosmetic,
40-50% by weight concentrated alcohol aqueous solution, cleansing foam, lotion, milky lotion, essence, hair,
Used for body. Also, it is dissolved in squalane and used for creams, emulsions, gels, make-up and the like.

In order to uniformly dissolve the high-quality wood vinegar liquid material in squalane, it is preferable to dissolve it in the presence of a surfactant. In this case, the preferred amount is 1 part by weight or less, more preferably 0.5 part by weight or less based on 100 parts by weight of squalane.

As a commonly used surfactant, it is preferable to use a natural surfactant in consideration of the effect on the living body.
Soybean: lecithin, egg yolk: phosphadylserine, phosphadylethanolamine, phosphadylcholine and the like. In addition, commonly used anionic surfactants: higher fatty acid soaps, alkyl sulfates, polyoxyethylene alkyl sulfates, acyl N-methyltaurine salts, alkyl ether phosphate salts, N-acyl amino acid salts, cationic surfactants: Alkyltrimethylammonium chloride, dialkyldimethylammonium chloride, belesalkonium chloride, amphoteric surfactant: betaine alkyldimethylamine acetate, betaine alkylamidodimethylaminoacetate, 2-alkyl-N-carboxy-
N-hydroxyimidazolinium betaine, nonionic surfactants: polyoxyethylene type, polyhydric alcohol ester type, ethylene oxide / propylene oxide block copolymer polymer surfactants.

When utilizing the antibacterial effect of the raw material of high quality wood vinegar, it is usually used in the form of an ointment. Alternatively, it is used in the form of a cream or jelly.

The content of the high-quality wood vinegar liquid when used as the above-mentioned cosmetic, anti-pharmaceutical antibacterial agent or food additive is usually 0.1 to 50% by weight, more usually 1.0 to 1.0% by weight.
~ 3.0% by weight.

[0030]

The present invention will be further described below with reference to examples.
At the same time, the usefulness of the high-quality wood vinegar and high-quality bamboo vinegar raw materials obtained by the production method of the present invention will be described.

Example 1 The used crude wood vinegar contains harmful substances as shown in Table 1. Crude vinegar 100 weight activated carbon to adsorb the active ingredient (manufactured by Takeda Chemical Industries, Ltd., trade name Shirasagi) 2 parts by weight of additives and thoroughly stirred to crude vinegar solution under ordinary temperature. The pH of the aqueous phase at the time of mixing was 2.4. After standing overnight, 0.
Suction filtration was performed using a filter having a pore size of 8 μm to obtain an activated carbon adsorbate. This activated carbon adsorbate is added to water 1
After 0 parts by weight of the added activated carbon adsorbate was crushed to obtain a homogeneous phase, the mixture was suction-filtered again to obtain a washed activated carbon adsorbate.

Then, ethyl alcohol was added to the adsorbate.
100 parts by weight of a 1: 4 mixture of ethyl acetate was added, and the mixture was crushed to obtain a uniform product. Then, the mixture was subjected to suction filtration using the above-mentioned filter to extract and transfer a useful substance to a mixed liquid phase. The adsorbed material separated here was again disintegrated with the same amount of the mixed solution to obtain a uniform product, and then subjected to solid-liquid separation.

The obtained two extracts were mixed and evaporated to dryness with a rotary evaporator to obtain a high-quality vinegar liquid material. The high quality wood vinegar liquid raw material obtained by this production method was usually in the range of 0.76 to 0.80 g per 100 ml of the crude wood vinegar liquid.

[0034] The chemical components of the high-quality wood vinegar raw material obtained Mamoru
With raw test method and commentary 1990. Supplement (1995) Household goods
The analysis was carried out according to the various test methods described in the test method "Perfume test method", and the results are shown in Table 1 together with the chemical components of the raw crude wood vinegar solution.

Comparative Example 1 Ethyl alcohol-acetone (1: 4) was used in place of ethyl alcohol-ethyl acetate (1: 4) used in Example 1 for extraction and treatment in the same manner as in Example 1.

[0036]

[Table 1] (*) Chemical components of a solution prepared by dissolving a high-quality wood vinegar solution raw material manufactured using 100 ml of crude wood vinegar solution in 100 ml of a 50% ethyl alcohol solution.

Application Example 1 Antibacterial action of high quality wood vinegar

Example 1 Using 100 ml of crude wood vinegar,
The antibacterial effect of a high-quality wood vinegar solution prepared by dissolving a high-quality wood vinegar solution raw material prepared according to the above method in 100 ml of a 50% ethyl alcohol solution was examined. Table 2 shows the results. % In Table 2
Indicates the effective dilution concentration of a 50% ethyl alcohol aqueous solution.

[0039]

[Table 2] Staphylococci (S) that cause superficial skin and mucosal infections
taphyloccous arureusu (MRSA) with a high quality wood vinegar solution of 3.12% or more, and Pseudomonasaeruginos
More than 6.24% for a) and more than 12.5% for Candida albicans, Trichophytium
on mentagrophytes) and more than 3.12% against the pathogenic E. coli O-157,
Antimicrobial activity was observed at a concentration of 3.12% or more against the pathogenic bacterium Escherichia coli O-157, which is a representative bacterium of food poisoning.
As a result, high-quality wood vinegar does not contain formaldehyde and methanol and exhibits antibacterial activity against certain pathogenic microorganisms. It can be expected as a topical remedy or a natural safe disinfectant for foods.

Application Example 2 A wide range of ultraviolet rays of 250 to 400 nm has reached the ground. As toxic effects of the ultraviolet rays, erythema, tanning, blackening, aging of the skin, and the like are known. 5
High quality wood vinegar solution dissolved in 0% ethyl alcohol solution,
The result of diluting with ethyl alcohol, measuring the absorbance at a wavelength of 200 to 400 nm, and examining the ultraviolet absorbing ability is shown in FIG. The high-quality wood vinegar solution contains a component exhibiting a maximum absorbance at a wavelength of 270 to 280 nm.
It has the ability to absorb ultraviolet light of B, and is identified as a phenolic substance from the characteristics of the absorption curve using a standard substance.

In order to give a cosmetic preparation containing a high-quality wood vinegar liquid a broader ultraviolet absorbing ability, an ultraviolet absorbent having a maximum absorbance at 320 to 380 nm, such as Parsol A, may be added.

Application Example 3 A high-quality wood vinegar liquid raw material produced according to the method for producing a high-quality wood vinegar liquid is dissolved in squalane as in the following A) and B) to obtain a cosmetic compounding material (high-quality wood vinegar liquid squalane). Solution) in a ratio of 3 parts by weight of a high quality wood vinegar liquid squalane solution to 97 parts by weight of white petrolatum at a temperature of 75 to
The mixture was heated and mixed at 80 ° C. to prepare a high-quality wood vinegar liquid vaseline ointment, and a human patch test was performed to confirm its safety. The subjects were 43 men and women in total. The test site is the upper back, and the test method is the safety of new raw materials as described in the Ministry of Health, Labor and Welfare's "Production of cosmetics incorporating new raw materials or the range of safety data to be attached to import applications" notified on August 18, 1987. In accordance with the human patch test of test items (guidelines) to ensure Table 3 shows the test results.

[0043]

[Table 3] A) A raw material of high quality wood vinegar produced by adsorbing 100 ml of crude wood vinegar on activated carbon and dissolved in 100 ml of squalane in the presence of 0.5 g of soy lecithin as a natural surfactant.

B) shows a sample of A (3 ml) and white petrolatum 97.
g blended.

1) Positive erythema 2) Positive edema As shown in Table 3, both high-quality wood vinegar squalane solution and high-quality wood vinegar liquid petrolatum ointment showed skin changes such as erythema and edema at the sample application site. Did not. These results indicate that the high-quality wood vinegar liquid squalane solution and the high-quality wood vinegar liquid petrolatum ointment were found to be safe for human skin.

Application Example 4 The crude wood vinegar has an antibacterial action against various pathogenic microorganisms, and the high-quality wood vinegar purified therefrom also has a concentration difference, but like the crude wood vinegar, it is effective against certain pathogenic microorganisms. It has been confirmed that the compound has an antibacterial effect (Table 2).

In the microorganism identification test, Trichophyton mentagrop
Hytes was used to rub the affected area twice a day (in the evening at bedtime after taking a bath) against five men with ringworm tinea fungus diagnosed according to hytes on the affected area with the high quality wood vinegar liquid Vaseline ointment prepared in Application Example 3B. It was applied so as to fit. In the first five cases, the affected area had erosion and complained of itching. The effect was evaluated by visual observation and the complaint of each case in the second week.

In each case, the pruritus disappeared, the erosion of the trunk disappeared, and no scar was observed.

Conventionally, stubborn tinea pedis (commonly known as athlete's foot)
Corticosteroids are used as treatments for
It seems to have been completely cured, but the symptoms worsen, and pigmentation of the affected area, cracking of the skin of the affected area, abnormal drying, inflammation, and hyperkeratosis are often observed. Such aggravation of the symptoms is the same in the affected area where steroid therapy (application of corticosteroid to the trunk) is performed for atopic dermatitis.

The high-quality wood vinegar vaseline ointment, unlike adrenal corticosteroids as described above, has great promise as a safe therapeutic agent for tinea bacillosis and atopic dermatitis without side effects. Application Example 5 In the case of producing a high-quality wood vinegar liquid vaseline ointment or cosmetic oil (oil type) for preventing cracking of a katato or for repairing cracked skin.

3 g of high quality wood vinegar liquid squalane (product of application example 3A) is mixed with 97 g of white petrolatum at a temperature of 75 to 80 ° C.
The mixture was sufficiently mixed while heating with. To increase the softness if desired, it is possible to reduce white petrolatum and add squalane or jojoba oil that does not contain high quality wood vinegar.

As a cosmetic oil (oil type), a mixture of 30 g of liquid paraffin, 50 ml of olive oil, 3 ml of high-quality wood vinegar liquid squalane (the product of A in Example 3) and 17 ml of ordinary squalane was heated at a temperature of 70 to 85 ° C. And mixed well. It is also possible to add a favorite fragrance to this.

Application Example 6 In the production of a cosmetic for shaving, the high-quality wood vinegar liquid raw material produced in Example 1 is dissolved while adding purified water thereto while heating. The amount of purified water to be added is the same as the amount of the crude wood vinegar used.

55 ml of purified water is added to 40 ml of glycerin and 3 ml of a high-quality wood vinegar solution and mixed well. Since this liquid is odorless and colorless and transparent, it is possible to add fragrances and pigments as desired.

[0055]

According to the present invention, the active ingredient of wood vinegar is adsorbed on activated carbon by mixing crude wood acetic acid with activated carbon powder, and then adsorbed on activated carbon powder with a mixed solvent of ethyl alcohol and ethyl acetate. By extracting the active ingredient, the contact state becomes better than ethyl acetate alone or other organic solvent systems, and the extraction can be performed efficiently,
For example, it is possible to efficiently extract a high-quality wood vinegar liquid raw material that can be used as a compounding agent for cosmetics, medicines, and foods containing the active ingredient in the crude wood vinegar liquid by reducing the extraction of inactive ingredients such as wood tar.

[Brief description of the drawings]

FIG. 1 is an absorption spectrum of a high-quality wood vinegar solution obtained in Example 1.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI A61K 35/78 A61K 35/78 Y

Claims (1)

(57) [Claims] The crude wood vinegar is brought into contact with activated carbon powder under acidic condition of pH 2.5 or less to adsorb the active ingredient in the crude wood vinegar to activated carbon, and then the formaldehyde and methanol in the activated carbon layer are washed and removed with water. And elute the active ingredient in a mixed solvent phase in which the mixing ratio of ethyl alcohol and ethyl acetate is in the range of 1: 9 to 3: 7, and evaporate the organic solvent phase to dryness, thereby obtaining methyl alcohol and formaldehyde. Production method of high quality wood vinegar liquid raw material that does not contain.